This species occurs in the Andes, including in the inter-Andean valleys from Colombia through to Ecuador, to Huancabamba in Piura Department in northern Peru, from 2100-3300 masl. All records of this species from Venezuela are now assigned to Centrolene venezuelense.

In Ecuador, at Yanayacu Biological Station, only three individuals of Centrolene buckleyi were found after an intensive 3-year inventory effort, suggesting that that this species is quite rare at this locality (Guayasamin et al., 2006). Elsewhere in Ecuador (e.g. Pilaló) the species was formerly abundant; however, it is now absent from these localities (Bustamante et al., 2005; J.M. Guayasamin, pers. comm. 2008). It is still easily found in Colombia, while in Peru it is known only from two recent specimens.

The species lives in montane primary and secondary forests, in páramo bushland and grassland, and in terrestrial bromeliads in inter-Andean valleys. It is nocturnal, sometimes arboreal, and lays its eggs on leaves above streams, the larvae then develop in these streams. In Ecuador, C. buckleyi seems to reproduce in the months of April and May in permanent streams. One clutch was found to contain 18 eggs (J.M. Guayasamin, pers. comm. 2008).

It appears not to be affected by habitat loss, surviving in areas with heavy human impact. The serious decline in Ecuador is thought to be due to chytrid fungus. However, predictions suggest that, in Ecuador, almost half of the habitats suitable for this species have been deforested (Cisneros-Heredia, 2008).